Process of dyeing



Patented Nov. 18, 1941 PROCESS OF DYEING Alva L. Honk and Louis H. Bock,Philadelphia,

Pa., assignors to 8; Haas Company,

Philadelphia, Pa.

No Drawing. Application July 7, 1939, Serial No. 283.140

7 Claims.

This invention relates to a process of dyeing in 1 which fixation ofdyestufi on textile material is improved. It relates in particular tothe fixation of certain dyestuifs by condensing them with formaldehydeand a non-aromatic, primary or secondary amine, impregnating textilematerial.

therewith, and subsequently heating the impregnated material to causethe dyestufi condensate to combine with the textile material.

The object of this invention is to improve the fastnessof certaindyestuffs, herein called methylol-forming, on textile materials. It isanother object of this invention to provide a process for imparting todyed fibers, yarns, and

fabrics a high degree of resistance to removal of dye from cleaningduring laundering, and dry cleaning or from wear. It is also an objectto provide a process for dyeing which does not require the use of amordant. It is another object to provide dyestufis by which color may beimparted to different types of fibers by the same dye. A further objectis to provide a universal one-bath dyeing process.

Fixation of certain dyestuffs may be accom-' plished by processingtextile material with a dyestuif possessing the group in which Arrepresents an aromatic nucleus carrying a nuclearly-bound oxygen orsulfur atom, A

represents a member of the group consisting of hydrogen, and aliphaticand alicyclic radicals, and B represents a member of the groupconsisting of aliphatic and alicyclio hydrocarbon groups. A and B mayrepresent, when taken jointly, a divalent hydrocarbon radical or adivalent heteroradical which jointly with the nitrogen forms aheterocyclic ring, such as found in piperidine, piperazine, pyrrolidine,morpholinc, and other cyclic,'basic, secondary amines. This essentialfixative group may be formed in any dyestuff which is capable ofreacting with formaldehyde to form a methylol compound. Aromaticcompounds which possess a phenolic hydroxyl or sulfhydryl group withpositions available for substitution ortho or para to the hydroxyl orsulfhydryl group are known to react with formaldehyde and are commonlydesignated methylolforming phenols. The term methylol-forming dyestufior dye is used in the same sense and is applied to those dyestuffs whichhave available for substitution ortho or para positions relati e to anuclearly-bound phenolic hydroxyl or sulfh'ydryl triethylene tetramine,and the like.

pregnate fibers, yarn,

non-aromatic amines possessing at least one hy-' drogen held bythenitrogen atom and are operable in this process.

Methylol-forming dyestuflfs are thus reacted with formaldehyde andamines and used to imbatting, or fabric by paddipping, spraying, orprinting according to such well known methods as skein-dyeing,chaindyeing, raw stock dyeing, package dyeing, piece dyeing, rollprinting, screen printing, and the like.

Excess dyeliquor may be removed by any suitable means. such as squeezerolls, centrifugal extractor, or the like, when so desired; Then, withor without previous drying, the impregnated material is subjected to atemperature high enough to bringabout a reaction ofthe dyestuif and thetextile material. The required temperatures are above C. The temperatureused will depend upon the material being dyed, the

dyestuff, the process of treating, the presence completing the reaction.At temperatures of to C. a; few minutes usually sufllces to fix thedyestufi. At temperatures below 120 C. longer times are necessary, eventimes up to an hour being sometimes required. After the reaction oforganic fiber and modified dye has been eifected,- it is usuallydesirable to washthe treatedmaterial to remove unreacted excess dye,soluble reaction products, etc.,' as in the usual soaping-ofi procedure.

The dyes which are amenable to fixation by this process are mostconveniently classified according to chemical structure and include azodyes, such as Tannin Orange R (basic) Resorcin Yellow (acid),Betanaphthol Orange (acid). Para Red (acid), Sudan III (a disazo dye)etc.; nitroso dyes, such as Resorcin Green; indophenol dyes, such asIndophenol Blue (basic); hydroxyketone dyes, such as Alizarine Yellow C,Flavopurpurin, alizarinirisol, etc.; indanthrene dyes, suchasIndanthrene Blue 5G; triphenyl methane dyes, such as fiuorescein,aurine, xanthene, etc.

The secondary amines which are effective in this process are aliphatic,heterocyclic'and alicyclic amines of a wide range of molecular size andstructure. Examples of secondary amines which maybe used includedimethylamine, diethylamine, dibutylamine, diamylamine, methyldodecylamine, dicyclohexylamine, morpholine, piperidine, piperazine,pyrrolidine, diethanolamine,

Primary amines are also eflective in-our process. Typical compoundsinclude. monomethyh amine, monoethylamine, ,t-amy'lam'ine, caprylamine,cyclohexylamine, ethylenediamine, monoethanolamine, etc. It is possiblewith primary amines to use more than one equivalent of iormaldehyde foreach equivalent-of amine to obtain various products of structureswhich-have not been determined.

In general the condensation of a .methylolforming dye with formaldehydeand a primary or a secondary amine is performed under conditions whichdo not greatly alter the dye or lessen its value as a dyestufl. Reactingproportions of the materials aremixed. It is often advantageous to 1 usean inert solvent, such as alcohol,-water, ether,

dioxane, or benzene. The mixture may the allowed to stand fortwenty-four hours'or more at room temperature or the may be heated underreflux or :in a closed vessel. If desired, the formaldehyde and aminemay be mixed first and the dye added in successive increments. Inanother procedure dye and amine may be mixed and formaldehyde solutiongradually added. The product may be separated by .distilling of! thesolvent. It may sometimes be separated .by crystallization. It is alsopossible to use the dye solution directly without .further treatment forpurification.

It is necessary to use at least one "molecular equivalent offormaldehyde and at least one'molecular equivalent of an amine for .eachmolecule of dye. When more than one :reactive ortho or para position ina phenolic nucleus'is available for substitution, more than oneequivalent each of formaldehyde and aminemay beused, if desired, tointroduce two or more methylene amine groups.

The reacted dye may be .app'liedin the same way as anycomparabledyestuif. It maypbe used in the presence of an acid, such asacetic acid, in which case a salt form is applied. It may, if desired,be used in the presence of :an alkaline material, such as soda ash,sodium bicarbonate,

In applying the modified dyestuffs 2 small I 55 amounts of an acid or anacidic salt seem to provide catalytic action in the reaction o1 thedye'and textile material, but they are not essential in the process.

methylene amine .group in the dye is the improved solubility or.dispersibility of many or the treated :dya. Furthermore, any of thedyes obtained by the herein described method may be reacted withpractically any natural or artificial fiber which contains reactivegroups, such as the hydroxyl groups in cellulosic materials. It does notfollow that identical shades result on all types of fibers, but thetreatment does allow the use of dyes on fibers which would otherwise notbe receptive to a particular dye. Likewise, dyes which are not otherwisetest may be applied.

The following examples illustrate the preparatiomof dyes used in thisprocess:

"Pansiwrron A.-Dimethylaminomethyl fluorescein To 16.6 g. of fluoresceinin 150 ml. of water was added a solution containing 20 g. of 30% formal-.dehyde and 36 :g. of 25% dimethylamine. This was stirred at 70 C. for 3hours. The solution becamedark red when concentrated, and green- .ishyellow when very dilute. Acid changed it to green in any concentration.It was concentrated in vacuo at C. to a brittle, light red solid. It wasmore soluble in water than was fluorescein. Nitrogen analysis was 7.07%,showing it to contain slightly more than two dimethylaminomethyl groups.

PREPARATION B.Benzyl chloride quaternary salt of dimethylaminomethylfluorescein To 5 g. of dimethyl aminomethyl fluorescein was added 4 g.of benzyl chloride with thorough mixing. This mixture was heated on thesteam bath for 2 hours. It became gummy,- then brittle, and yielded ared powder which contained 4.08% nitrogen.-

Pasrans'rron C.-Morpholinomethyl 3-amino-4- methylbenzeneazo-a-naphtholTo 9.2 g. of 3-amino-4-methylbenzeneazo-anaphthol was added a solutioncontaining 7 g. of 15% formaldehyde and 3.4 g. of morpholine and 50 ml.of water. These were stirred together for 3 hours at 70 C. andconcentrated in vacuo at 50 C. A red powder resulted, soluble in diluteacids.

"PREPARATION ,D.P1'oduct from quinizarin, formaldehyde andmonomethylamine To 24 g. oi quinizarin suspended in- 150 ml. of

' water was added g. of 35% aqueous monomethylamine and.20 g. of 30%aqueous Iorma1dehyde. The mixture was stirred at C. for 3 hours.Concentration in vacuo at 50 C. gave a dark brown powder, containing3.68% nitrogen. It; was soluble in amine solutions or other basicsolutions and to a limited extent in dilute acids.

The dyestufls bearing a methylene amine group react with a wide varietyof organic textile materials, such as -wool, silk, cotton, mercerizedvcotton, rayon, cellulose acetate, paper, linen, kapok, jute, straw,etc. These materials may be in the form of fibers, or raw stock, yarn,,woven or knitted cloth, felts, batting, etc. Any of the organicmaterials which are used in making fabrics, yarns, sheets, battings, andthe like, and

which are not damaged by treatment in an equeous bath and by heatingabove 100 C. may be used in'the herein described process. The textilematerial and the modified dye react, it is believed, through themethylene group, which has been added to the dye, and yield a complexwhich resists removal of dye by any ordinary means. Another advantagevof the introduction of the Details or various typical applications are-givn herewith to illustrate the wide application oi the new dyeingprocedure.

' 1 1 Example 1 pieces of cotton, silk, and wool were dipped in a 5%aqueous solution of bis-dimethyl- .aminomethyl' fluorescein, squeezedand dried.

They were then heated at'l30 C. for one-half hour and given a thoroughwashing. Colors were Wool and cotton fabrics were treated as in ExampleNo. 1, except that the benzyl chloride aaeaser 3 quaternary salt ofdimethylaminomethyl nunrescein was used in aqueous solution. I

After being heated at about 130 C. and washed, the cotton waspermanently d'yed a bright yellow-orange, and the wool a pale peachshade.

Example 3 Cotton, silk, and wool fabrics were run through a bath of a 5%aqueous solution of bis-dimethylaminomethyl 3,6-dihydroxy-9-phenylxanthene containing a trace of acetic acid. They were squeezed, dried,and heatedone-half hour at 130- C. After being washed, the cotton andsilk were deep rose-red, and the wool was pale rose.

Example 4 Cotton, silk, and wool fabrics were run through a 1% alcoholicsolutionof dimethylaminomethyl 3-amino-4-methyl benzene-azo-a-naphthol,and

subsequently treated as in Example 3. All retained arich chocolate browncolor after thorough washing.

Example 5 Cotton, linen and wool samples were treated as in Example 3,except that the dye used was a -2% aqueous solution ofdimethylaminomethyl quinizarin as the acetate. The colors produced weredeep purple on cotton and linenand medium purple on the wool.

Example 7 A viscose rayon fabric was treated with a solumols of aqueousmonomethylamine. It was dried, heated one-half hour at 130 C.,andwashed. A deep purple color was retained.

7 process of this application may be substituted for the sulfonation. Inthis way the dye is obtained in a soluble form and atthefsame time thenew method of fixing'thedye may be used. However, sulfonated dyes can '1be used in the process 'By condensing a methylol' forming dye withformaldehyde and a non'l-aromatic amine having at least one hydrogen oneach nitrogen atom, thereis obtained a dye'stu'if' which may be fixed toan organic textile matcrial'by the application of heat. Certain dyes notpreviously retained by fibres may thus be applied without the use ofmordants or precipitating agents. -;Dyes which were heretoforeretainedonly by one type of fibre may be used with other'types as well. Only asingle dye-bath is required in processing and the process of fixation ofdyes herein described may be carried out with the equipment available inpractically any finishing and dyeing plant.

vPhenolic dyestuffs which have been avoided betion ofbisdimethylaminomethyl 3,6-dihydroxy- 9-pheny1 xanthene as in Example 3.,It retained a rose-red color, fast to washing.

Example 8 A cellulose acetate fabric was run through a alcoholicsolution of dimethylaminomethyl 3-amino-4-methyl benzeneazonaphthol,squeezed, dried, and heated one-half hour at 130 C. After washing, thecolor was cocoa-tan.

- Example 9 Pieces of linen fabric were dipped through an aqueoussolution containing 2% of dimethylaminomethyl quinizarin and 2% ofacetic acid.

They were treated as in Example 8. A'deep bluepurple color resulted.

Example 10 cause of sensitivity to alkaline soaps may be used in our newprocess of dyeing. This is particularly true of vat dyes containingphenolic hydroxyl groups. The treatment usually improves solubility anddispersion of dyes and thus increase their effectiveness in application.

We claim:

1. The process of fixing on organic textile material a phenolic dyestuffhaving available for substitution at least one hydrogen atom in the Poitions ortho and para to the aromaticallybound hydroxyl group, whichcomprises condensing said dyestuifwith formaldehyde and a non-aromaticamine, having at least one hydrogen atom held by the nitrogen atom, toform a methylene amine condensatewiththe dyestufi, applyingsaid'condensate to textile material, and heating the treated textilematerial until the modified dy'estufl is fast thereto.

2. The process of fixing on organic textile material a phenolic dyestufihaving available for substitution at least one hydrogen atom in the solthe dyestuif bearing a methylene amine group to stufi is fast'thereto.

3. The process of fixing on organic textile material a phenolic dyehaving available for substitution at least one hydrogen atom in thepositions ortho and para to the aromatically-bound 3 hydroxyl group,which comprises condensing said -dye with at least one mol equivalenteach of retained a deep rust shade and the mohair was a lightly colored,giving an attractive effect of differential dyeing.

Example 11 A cotton sheeting was dipped through a solution containing10% of acetic acid and about of the product from the reaction ofquiniformaldehyde and of a non-aromatic, strongly basic, secondaryamine, applying the condensate thus formed to'textile material, andsubsequently heating the textile material carrying the condensate above100 C.

4. The process of fixing on organic textile material a dyestuff,possessing a hydrogen atom in a position ortho or para to anucleariy-bound hydroxyl group, which comprises condensing said dyestuffwith at least equivalent proportions each of formaldehyde and of anon-aromatic,

zarin with 2 mols of aqueous formaldehyde and 6 strongly basic,secondary amine,- to form a methmaterial a phenolic dye having availablefor substitution at least one hydrogen atom in the positions ortho andpara to the aromatically-bound hydroxyl group, which comprisescondensingsaid dye with at least one mol equivalent of formaldehyde and.at least one mol equivalent of di-] applying the condensate thus; formedto textile material and heating the treat-' methylamine,

ed textile material above 100 C.

6.,The process of fixing onjorganic textile material a phenolic dyehaving. available for substitution at least one'hydrogen atom in thepositions ortho and para to .'the 'aromaticallybound hydroxyl group,which, comprises condensing said dye with at least one mol equivalent offormaldehyde and at least one mol equivalent or monomethylamine,applying the condensate thus formed to textile material and heating thei 5 treated textile material above 100 C.

7. The process of fixing on organic textile material a phenolic dyehaving available for substitutionat least one hydrogen atom-in thepositions ortho and para. to the aromatically- 1 bound hydroxyl group,which comprises condensing said dye with formaldehyde and a nonaromatic,secondary amine to form a methylene amine condensate, allrylating saidamine condensate to form a quaternary ammonium salt,

15 aPDh'ing said salt to'dye said textile material,

and heating the dyed textile material until the v modified dyestufl' isfast thereto.

ALVA L. HOUK.

LOUIS H. BOCK.

